CN104399974A - Continuous control method for gold nanometer particle aggregate microstructure - Google Patents

Continuous control method for gold nanometer particle aggregate microstructure Download PDF

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Publication number
CN104399974A
CN104399974A CN201410777946.9A CN201410777946A CN104399974A CN 104399974 A CN104399974 A CN 104399974A CN 201410777946 A CN201410777946 A CN 201410777946A CN 104399974 A CN104399974 A CN 104399974A
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nanometer particle
dna
golden nanometer
gold nanometer
microstructure
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CN201410777946.9A
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代昭
金萍
杨秋风
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Abstract

The invention discloses a continuous control method for a gold nanometer particle aggregate microstructure. The method comprises the following steps: preparing gold nanometer particles which are uniform in particle size by using sodium citrate to reduce chloroauric acid; adding bi(p-sulfonyl phenyl) phenyl dipotassium phosphine to improve the stability of the gold nanometer particles; performing surface modification on the gold nanometer particles which are different in particle size by using single-chain DNA modified by different sequential sulfydryl; bridging the two types of single-chain DNA modified gold nanometer particles by using a DNA extension connector to obtain a gold nanometer particle aggregate. The microstructure of the gold nanometer particle aggregate can be continuously controlled by precisely controlling the proportion of the DNA extension connector so as to prepare a gold nanometer particle dipolymer, a gold nanometer particle tripolymer and a gold nanometer particle tetramer which are of a continuous microstructure and the ratios are respectively 1:1, 1:2 and 1:3.

Description

A kind of continuous control method of golden nanometer particle aggregate microstructure
Technical field
The present invention relates to the preparation method of field of nanometer technology, be specifically related to a kind of method can carrying out continuous control to the microstructure of golden nanometer particle aggregate.
Background technology
Golden nanometer particle (Gold Nanoparticles, AuNPs) because it possesses unique optical, electrical character, chemical stability, catalytic activity, bioaffinities etc., study at SERS, catalysis, electrochemistry, ion detection, plays the effect become more and more important in the field such as medical diagnosis and biology sensor.Utilize in recent years, the golden nanometer particle aggregation building different types of structure is devoted in increasing research, studies its optical and electrical properties, to explore the application of golden nanometer particle in nano science further.
At present, prepare golden nanometer particle aggregate to need to use the double-strand hybrid dna (dsDNA) of sulfydryl modification to put up a bridge between golden nanometer particle as connector, this needs first to use the single stranded DNA of two kinds of base sequence complementary (ssDNA) to modify golden nanometer particle, then utilizes the hybridization between two kinds of ssDNA to form dsDNA and coupled together by golden nanometer particle to form golden nanometer particle aggregate.And ssDNA is when modifying golden nanometer particle, because golden nanometer particle surface has the more site that can react, therefore cause the final single stranded DNA quantity that connects in each golden nanometer particle surface and heterogeneity, and this is generally the mixture with various different particle ratios (i.e. microstructure) by causing the golden nanometer particle aggregate finally obtained.
The continuous control method of golden nanometer particle aggregate microstructure of the present invention, utilize two hydrations two (p-sulfonyl-phenyl) Phenylphosphine di-potassium (BSPP) as golden nanometer particle stabilizing agent, improve the dispersiveness of golden nanometer particle in water and stability, DNA prolongation connector instead of traditional double-strand hybrid dna is used to carry out bridge joint between golden nanometer particle, when accurately control DNA extends connector ratio, continuous print control can be carried out to the microstructure of golden nanometer particle aggregate, namely prepare and have 1: 1, 1: 2, the gold nanoparticle dimer of the continuous type such as 1: 3, tripolymer and the tetramer.
Summary of the invention
(1) technical problem that will solve
Technical problem underlying to be solved by this invention is by using BSPP as the stabilizing agent of golden nanometer particle, and use DNA prolongation connector to carry out bridge joint to golden nanometer particle, by carrying out continuous control to the microstructure of golden nanometer particle aggregate when accurately control DNA extends connector and strand ssDNA input amount.
(2) technical scheme
Technical scheme of the present invention is: in aqueous phase, use reduction of sodium citrate gold chloride to prepare golden nanometer particle, uses BSPP to improve stability and the dispersiveness of golden nanometer particle as stabilizing agent.Use DNA to extend connector to modify the golden nanometer particle that strand ssDNA modifies respectively, the ratio extending connector by accurate control DNA, can control the microstructure of golden nanometer particle aggregate.
(3) concrete course of reaction
The continuous control method of golden nanometer particle aggregate microstructure of the present invention comprises the following steps:
1. prepare golden nanometer particle:
Intermediate water and precious metal salt (such as gold chloride) solution is added in the beaker boiled through intermediate water, sub-fluidized state is heated under stirring, add sodium citrate solution rapidly, continue to be heated to boiling, heating is stopped after keeping boiling 30min, after centrifugal, the golden nanometer particle obtained is scattered in intermediate water, changes the input amount of precious metal salt or natrium citricum, the golden nanometer particle of different-grain diameter can be prepared.
2. use BSPP to improve the stability of golden nanometer particle:
By the solution of the golden nanometer particle of preparation in step 1, add the BSPP aqueous solution of 40mg/mL, at 40 DEG C of reaction 1h, centrifugal after cooling, abandoning supernatant, adds 1mg/mL BSPP-0.5 × tbe buffer liquid, obtains the golden nanometer particle that BSPP is stable.
3. prepare the golden nanometer particle that strand ssDNA modifies:
The golden nanometer particle of sulfydryl modification strand ssDNA to different-grain diameter of following 2 kinds of base sequences is used to modify,
The sequence of ssDNA used is as follows
The golden nanometer particle of two kinds of different-grain diameters of preparation in step 2 (is designated as Au respectively 1and Au 2, Au 1and Au 2particle diameter can identical also can be different), use ssDNA respectively 1and ssDNA 2modify, wherein control Au 1with ssDNA 1mol ratio be 1: 10 ~ 20, Au 2with ssDNA 2mol ratio be 1: 1,0.5 × tbe buffer the solution containing 0.01mol/L NaCl is dropped in the golden nanometer particle dispersion liquid that above-mentioned two kinds of different strand ssDNA modify, in 37 DEG C of reactions after 10 hours, adding the NaCl aqueous solution containing 2mol/L to the concentration of NaCl is 40mmol/L, react again after 24 hours and carry out centrifugation, obtain ssDNA respectively 1the Au modified 1(be designated as Au 1-DNA 1) and ssDNA 2the Au modified 2(be designated as Au 2-DNA 2), the buffer solution both being put into 0.5 × TBE saves backup at 4 DEG C.
4. the preparation of golden nanometer particle aggregation:
DNA extends connector and is formed by two kinds of strand ssDNA hybridization, and the base sequence of these two kinds of strand ssDNA is as follows:
By Au 1-DNA 1with ssDNA 3the mol ratio mixed by 1: 1 mixes, and in 0.5 × tbe buffer liquid, lucifuge reacts 24 hours, due to ssDNA 3with DNA 1on 18 base complementrities, therefore it can with DNA 1hybridize, and remain outside 15 bases will be exposed to, obtain ssDNA by centrifugation 3the Au modified 1-DNA 1(be designated as Au 1-DNA 1-DNA 3).Identical method is used to prepare ssDNA 4the Au modified 1-DNA 1(be designated as Au 2-DNA 2-DNA 4).By the Au of difference amount 1-DNA 1-DNA 3with Au 2-DNA 2-DNA 4put into respectively in 0.5 × tbe buffer solution, after being placed in each autoreaction 10h of constant temperature gas bath oscillator, the two mixing being continued in constant temperature gas bath oscillator and reacts 24h, namely obtain golden nanometer particle aggregate.Due to Au 1-DNA 1-DNA 3the base sequence exposed and Au 2-DNA 2-DNA 4the base sequence complete complementary exposed, therefore golden nanometer particle aggregate is obtained by the hybridization bridging effect of the two, and this golden nanometer particle aggregate can be made up of Au1 and Au2 two kinds or a certain golden nanometer particle, by the mol ratio of accurate control ssDNA3 and ssDNA4, can the ratio (microstructure) of accurate control Au1 and Au2.
Accompanying drawing explanation
Fig. 1 to be the microstructure of the embodiment of the present invention 1 gained be 1: 1 golden nanometer particle aggregate.
Fig. 2 to be the microstructure of the embodiment of the present invention 1 gained be 1: 2 golden nanometer particle aggregate.
Fig. 3 to be the microstructure of the embodiment of the present invention 1 gained be 1: 3 golden nanometer particle aggregate.
Specific embodiments
Be below specific embodiments of the invention, described embodiment is for describing the present invention, instead of restriction the present invention.
Embodiment 1
(1) synthesizing particle diameter is 40nm (Au 1) and 15nm (Au 2) golden nanometer particle
In the beaker of two 400mL, respectively add the ultra-pure water of 200mL, respectively add the aqueous solution of chloraurate of 3mL1%, heating, the sodium citrate aqueous solution of 1% of 3mL and 15mL is added rapidly respectively during state of boiling to Asia, be heated to boiling, continue heating 30min, room temperature is lower to be cooled naturally.Afterwards respectively with the centrifugal 25min of 7000r/min and 9000r/min, after abandoning supernatant, add a certain amount of ultra-pure water, the Au that particle diameter is 40nm can be obtained respectively 1with the Au of 15nm 2, in 4 DEG C of preservations.
(2) golden nanometer particle is stable
Get the Au in 1mL step (1) 1and Au 2aqueous dispersion be placed in the little centrifuge tube of 5mL respectively, respectively add the BSPP aqueous solution of 200 μ L40mg/mL, be placed in 40 DEG C of water-baths and react 1h, after room temperature cools naturally, respectively with 7000r/min and 9000r/min centrifugation 25min, after abandoning supernatant, respectively adding 1mL concentration is 1mg/mL BSPP-0.5 × tbe buffer liquid, after reacting 15h under room temperature, respectively at 7000r/min and 9000r/min centrifugation 25min, abandon supernatant, respectively add the BSPP-0.5 × tbe buffer liquid of 200 μ L 1mg/mL, in 4 DEG C of preservations.
(3) golden nanometer particle of strand ssDNA modification
The Au of gained in step (2) 1the ssDNA of 20 μ L, 5 μm of ol/L is added in aqueous dispersions 1, to Au 2dispersion liquid in add the DNA of 20 μ L, 5 μm of ol/L 2then NaCl 0.5 × TBE solution of 1mL 0.01mol/L is respectively added, after room temperature reaction 10h, point to add the NaCl aqueous solution of 4L2mol/L for five times, per hourly add once, add 20 μ L altogether, after at room temperature reacting 24h, respectively with 7000r/min and 9000r/min centrifugation 25min, after abandoning supernatant, respectively add 0.5 × tbe buffer liquid of 1mL, can Au be obtained 1-DNA 1and Au 2-DNA 2each three groups of solution.
(4) preparation of golden nanometer particle aggregation
The Au of gained in step (3) 1-DNA 15 of 1 μ L are added in dispersion liquid μthe ssDNA of mol/L 3solution, at Au 2-DNA 2the DNA of 1 μ L, 5 μm of ol/L is added in dispersion liquid 4solution, is placed in constant temperature gas bath oscillator respectively after 25 DEG C of isothermal reaction 10h, respectively at the centrifugal 25min of 7000r/min and 9000r/min, after abandoning supernatant, obtains DNA respectively 3the Au modified 1-DNA 1(Au 1-DNA 1-DNA 3) and DNA 4the Au modified 2-DNA 2(Au 2-DNA 2-DNA 4), after respectively adding 400 μ L0.5 × tbe buffer liquid, by Au 1-DNA 1-DNA 3and Au 2-DNA 2-DNA 4mix, be placed in 25 DEG C of constant temperature gas bath oscillators and react 24h, obtain the aggregate of golden nanometer particle, wherein, in each golden nanometer particle aggregate, only have 1 Au 1and Au 2, namely now the microstructure of golden nanometer particle aggregate is 1: 1.
Embodiment 2
Au in Example 1 1-DNA 1dispersion liquid 1mL, adds the ssDNA of 2 μ L, 5 μm of ol/L 3solution, at Au 2-DNA 2the DNA of 1 μ L, 5 μm of ol/L is added in dispersion liquid 4solution, be placed in constant temperature gas bath oscillator respectively after 25 DEG C of isothermal reaction 10h, respectively at the centrifugal 25min of 7000r/min and 9000r/min, abandoning supernatant, after adding 400 μ L 0.5 × tbe buffer liquid respectively, by two kinds of dispersion liquid mixing, be placed in 25 DEG C of constant temperature gas bath oscillators and react 24h, obtain the aggregate of golden nanometer particle, now in each golden nanometer particle aggregate, only have 1 Au 1with 2 Au 2, namely now the microstructure of golden nanometer particle aggregate is 1: 2.
Embodiment 3
Au in Example 1 1-DNA 1dispersion liquid 1mL, adds the ssDNA of 3 μ L, 5 μm of ol/L 3solution, at Au 2-DNA 2the DNA of 1 μ L, 5 μm of ol/L is added in dispersion liquid 4solution, be placed in constant temperature gas bath oscillator respectively after 25 DEG C of isothermal reaction 10h, respectively at the centrifugal 25min of 7000r/min and 9000r/min, abandoning supernatant, after adding 400 μ L 0.5 × tbe buffer liquid respectively, by two kinds of dispersion liquid mixing, be placed in 25 DEG C of constant temperature gas bath oscillators and react 24h, obtain the aggregate of golden nanometer particle, now in each golden nanometer particle aggregate, only have 1 Au 1with 3 Au 2, namely now the microstructure of golden nanometer particle aggregate is 1: 3.

Claims (3)

1. the continuous control method of a golden nanometer particle aggregate microstructure: it is characterized in that the stabilizing agent of use two hydration two (p-sulfonyl-phenyl) Phenylphosphine di-potassium (BSPP) as golden nanometer particle.
2. the continuous control method of a golden nanometer particle aggregate microstructure: it is characterized in that using DNA to extend connector carries out bridging connection to the golden nanometer particle that single stranded DNA is modified.
3. the continuous control method of a kind of golden nanometer particle aggregate microstructure according to claim 2, is characterized in that described DNA extends connector and can be strand or double-stranded DNA.
CN201410777946.9A 2014-12-16 2014-12-16 Continuous control method for gold nanometer particle aggregate microstructure Pending CN104399974A (en)

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Cited By (2)

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CN106596971A (en) * 2016-12-16 2017-04-26 江南大学 Precious metal plasma effect enhanced up-conversion fluorescence structure-based method for hypersensitive detection of vascular endothelial growth factor
CN113292050A (en) * 2021-07-02 2021-08-24 安徽农业大学 Novel nano-selenium double-ball and preparation method thereof

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CN106596971A (en) * 2016-12-16 2017-04-26 江南大学 Precious metal plasma effect enhanced up-conversion fluorescence structure-based method for hypersensitive detection of vascular endothelial growth factor
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